Diazonium



page 258) and a p tetrafiuoride (Znli r) H anorganische Patented Oct. 6,193i srarss VVINFBID I-IENT'RICH AND MAX HARDTMLANN, OFWIESDORF-ON-THE-RHINE, AND

ERNST 'rrnrzn, or oorioennon-Tr-IE-nrrmn, GERMANY, AssIeNons TO GENERALANILINE Worms, Inc, nnw n. oonrcna'rion or DELAWARE DIAZONIUIVI SALTS OFCOMPLEX METALLO I-IYDROFLUORIC ACID No Drawing. ApplicatTon filed lviay10, 1929, Serial No. 362,128, and in Germany April 3, 1928.

"The present invention relates to diazonium salt-s otcomplenmetallo-hydrofiuoric acids and to a process or preparing the same.

In accordance with the invention, diazonium salts of com lex.metallo-hydrofluoric acids are prepared by causing a complexnietallohydrofluoric acid (compare Zeitchritt tiir anorganische Ohemie,volume 19, page 158.: ibid. vol. 81, page 13; ibid. vol. 61, diazocompound to react upon each other. Acids of the kind specified are, forexample titanis dihydrohexafluoride (TiF H (Journ. fur praktischeChemie, vol. 81, page 556) aluminum trihydrohexafluoride (AlFQH (c. f.Gmelins Handbuch der anorganischen Chemie, 8th edition, sys tem number5, page 61) stannic dihydrohexafluoride (SnF )H (Gmelin, ibid. page 64)antinionous monohy drotetrafiuoride (SbFQ H (c. f. Pogg, Annalen derChemie, vol. 87, page 259) antimonic monohydrohexafluoride (SbF H(Zeitschrift fur anorganische Chemie, vol. 67, page 814:) and zinc.dihydro- (c. f. Zeitschritt :tiir Chemie, volume 3, pages 115 and 136).i

In carrying out our process we prepare a diazo solution in the customarymanner from any aromatic amine, and add thereto an about chemicallyequivalent quantity of a complex metallo-hydrofiuoric acid in aqueoussolution; generally we add a small excess of the complex acid. Theprocess is favorably carried out at low temperatures, say

at most about 25 C. and-in rather concentrated solution.

I O OH:

Likewise double decomposition of the salts of the complexmetallo-hydrofluoric acids with diazonium salts of the mineral acids inacid solution yields diazonium salts of the complex metallohydrofluoricacids. This process of preparing the new compounds is equivalent to thatdescribed above. It is worthy of note that well characterized stable 0diazonium salts can also be produced from such complex'metallo-hydrofluoric acids as 111 the free state are less stable orunstable.

Thediazonium salts of the complex metallo-hydrofiuoric acids generallyseparate in a crystalline form- They can be recrystallized from hotwater and dried with heat. They are completely insensitive, to rubbingand fairly so to percussion. Onheating they decompose without exploding;they are non-infiammableor burn with dilficulty. They are readilysoluble in water and in aqueous sol- Vents.

The diazonium compounds thus readily obtainable are intended to findapplication in dyein and printing and for combating insect pests.

The invention is illustrated by the following examples, without beinglimited thereto:

E sample 1 A. bisdiazonium chloride solution of the, highest possibleconcentration and obtained.

On treating the diazonium solutionIob- Example 2 tained from 19.7 gramsof -aminoaZobenzene, dilute hydrochloric acid and sodium nitrite with 30cc. of aqueous aluminum trihydroheXafluoride (45%), there separates abeautiful crystalline, stable diazonium compound, readily soluble inwater, which,'after filtering and drying, can be used as a stabilizeddiazotization product, for example for the production of dyeings onimpregnated fibers. The formation of the new diazoniuln 5 compoundprobably proceeds according to the following equation:

Instead of using the complex metallo-hydrotluoric acids in question, thesame can be produced in the reaction mixture or liberated from theirsalts.

We claim:

1. The process which comprises causing Exam/p103 22.3 grams of1-amin0-anthraquinone are diazotized with 7 grams Of SOdlllIl] nitrite(100%) in 30 cc. of sulfuric acid monohy- (Irate.- When thediazotization is complete, the mass is poured on to ice. The diazoniumsulfate precipitated is dissolved inwater with cautious heating andfiltered into 50 cc. of aqueous stannic dihydrohexafluoride (40%). Afterstrong coolin the diazonium hexafluorostannate, which srystallizes out,is filtered with suction and driedadvantageous-' ly in vacuo; The paleyellow salt is of satisfactory stability; It dissolves readily in water;the aqueous solution is fairly stable. The formation of the newdiazonium compound probably proceeds according to the followingequation:

1 Example 4 13.8 grams of 3-nitraniline are diazotized in the customarymanner. The diazonium so lution, as concentrated as possible, isfiltered andtreated with 25 cc. of aqueous antimonous 4omonohydrotetrafiuoride On strong coolin'g'the diazoniumtetrafiuoroantimonite separates in awell crystallized form. Itisfiltered with suction'and dried in vacuo, The yield amounts to 29 grams.The salt 45 is readil soluble in Water.

it'is er ectly stable. The formation of the new diazonium'compound'probably takes place according to the following equation:

NLC] Na .[SbFd co o a .304 [SnFo] HI (I CO 2 v C In the dry state zoniumcompound to react upon each other in aqueous solution.

3. The process which comprises causing about chemicallyequivalentquantities of titanicd-ihydrohexafluorie acid and a diazo Dllllllcompound to react upon each otherin aqueous solution.

l. The process which comprises causing about chemically cquivalentquantities of titanic 'dihydrohexaiiuoric acid and tetrazotized'dianisidine to react upon each other in aqueous solution.

5. As a dyest-ufi intermediates and insecti- 1 cidesythe diazoniulnsalts of complex metallohydrofluoric acids, being generally stable, wellcrystallizin'g substances, soluble in water.

6. As dyestuii' intermediates and insecticides, the diazonium salts ofcomplex titanic .hydrofluoric acids, being generally stable,

well crystallizing substances, soluble in water.

7. Asdyestufi" intermediates and insecticides, thQ/(lifiZOHlHIH salts oftitanic dihydrohexafiuoride, being generally stable, well crystallizingsubstances, soluble'in water.

8. As dyestufi" intermediate and insecticide, the hisdiazoni'um salt oftitanic dihydrohexafluoride and tetrazotized dianisidine, formingyellowish colored crystals, readily soluble in water.

In testimony whereol we have hereunto set our hands."

WINFRID nnN'ii-uoii. 1. 5. MAX HARDTMANN. [L.S.]

ERNST TIETZE. 1 5.

